Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization

Leonardo Maugeri; Tomas Lebl; David Bradford Cordes; Alexandra Martha Zoya Slawin; Douglas Philp

doi:10.1021/acs.joc.6b02822

Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization

Leonardo Maugeri, Tomas Lebl, David Bradford Cordes, Alexandra Martha Zoya Slawin, Douglas Philp

Research output: Contribution to journal › Article › peer-review

Abstract

Triphenylphosphine oxide forms halogen-bonded (XB) complexes with pentafluoroiodobenzene and a 1,4-diaryl-5-iodotriazole. The stability of these complexes is assessed computationally and by 31P NMR spectroscopy in d8-toluene solution, where both complexes are weakly associated. This knowledge is applied to the design and synthesis of two self-complementary phosphine oxide-iodotriazole hybrids that incorporate a phosphine oxide XB acceptor and a 1,4-diphenyl-5-iodotriazole XB donor within the same molecule. The self-complementary design of these modules facilitates their assembly in both d8-toluene and, surprisingly, d2-DCM into dimers, with significant stabilities, through the formation of halogen-bonded diads. The stability of these assemblies is a result of significant levels of cooperative binding that is present in both solvents. The connection of two of these hybrid units together, using a flexible spacer, facilitates the aggregation of these modules in d2-DCM solution, through halogen bonding, forming oligomeric assemblies.

Original language	English
Pages (from-to)	1986–1995
Number of pages	10
Journal	The Journal of Organic Chemistry
Volume	82
Issue number	4
Early online date	20 Jan 2017
DOIs	https://doi.org/10.1021/acs.joc.6b02822
Publication status	Published - 17 Feb 2017

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10.1021/acs.joc.6b02822

Philp,etal_2017_JoC_CooperativeBinding_AAM
Copyright © 2017 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1021/acs.joc.6b02822
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title = "Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization",

abstract = "Triphenylphosphine oxide forms halogen-bonded (XB) complexes with pentafluoroiodobenzene and a 1,4-diaryl-5-iodotriazole. The stability of these complexes is assessed computationally and by 31P NMR spectroscopy in d8-toluene solution, where both complexes are weakly associated. This knowledge is applied to the design and synthesis of two self-complementary phosphine oxide-iodotriazole hybrids that incorporate a phosphine oxide XB acceptor and a 1,4-diphenyl-5-iodotriazole XB donor within the same molecule. The self-complementary design of these modules facilitates their assembly in both d8-toluene and, surprisingly, d2-DCM into dimers, with significant stabilities, through the formation of halogen-bonded diads. The stability of these assemblies is a result of significant levels of cooperative binding that is present in both solvents. The connection of two of these hybrid units together, using a flexible spacer, facilitates the aggregation of these modules in d2-DCM solution, through halogen bonding, forming oligomeric assemblies.",

author = "Leonardo Maugeri and Tomas Lebl and Cordes, {David Bradford} and Slawin, {Alexandra Martha Zoya} and Douglas Philp",

note = "The authors thank the Marie Curie Initial Training Network on Replication and Adaption in Networks (ReAd) for financial support (early stage researcher funding to L.M.).",

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doi = "10.1021/acs.joc.6b02822",

language = "English",

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T1 - Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization

AU - Maugeri, Leonardo

AU - Lebl, Tomas

AU - Cordes, David Bradford

AU - Slawin, Alexandra Martha Zoya

AU - Philp, Douglas

N1 - The authors thank the Marie Curie Initial Training Network on Replication and Adaption in Networks (ReAd) for financial support (early stage researcher funding to L.M.).

PY - 2017/2/17

Y1 - 2017/2/17

N2 - Triphenylphosphine oxide forms halogen-bonded (XB) complexes with pentafluoroiodobenzene and a 1,4-diaryl-5-iodotriazole. The stability of these complexes is assessed computationally and by 31P NMR spectroscopy in d8-toluene solution, where both complexes are weakly associated. This knowledge is applied to the design and synthesis of two self-complementary phosphine oxide-iodotriazole hybrids that incorporate a phosphine oxide XB acceptor and a 1,4-diphenyl-5-iodotriazole XB donor within the same molecule. The self-complementary design of these modules facilitates their assembly in both d8-toluene and, surprisingly, d2-DCM into dimers, with significant stabilities, through the formation of halogen-bonded diads. The stability of these assemblies is a result of significant levels of cooperative binding that is present in both solvents. The connection of two of these hybrid units together, using a flexible spacer, facilitates the aggregation of these modules in d2-DCM solution, through halogen bonding, forming oligomeric assemblies.

AB - Triphenylphosphine oxide forms halogen-bonded (XB) complexes with pentafluoroiodobenzene and a 1,4-diaryl-5-iodotriazole. The stability of these complexes is assessed computationally and by 31P NMR spectroscopy in d8-toluene solution, where both complexes are weakly associated. This knowledge is applied to the design and synthesis of two self-complementary phosphine oxide-iodotriazole hybrids that incorporate a phosphine oxide XB acceptor and a 1,4-diphenyl-5-iodotriazole XB donor within the same molecule. The self-complementary design of these modules facilitates their assembly in both d8-toluene and, surprisingly, d2-DCM into dimers, with significant stabilities, through the formation of halogen-bonded diads. The stability of these assemblies is a result of significant levels of cooperative binding that is present in both solvents. The connection of two of these hybrid units together, using a flexible spacer, facilitates the aggregation of these modules in d2-DCM solution, through halogen bonding, forming oligomeric assemblies.

UR - http://pubs.acs.org/doi/suppl/10.1021/acs.joc.6b02822

U2 - 10.1021/acs.joc.6b02822

DO - 10.1021/acs.joc.6b02822

M3 - Article

SN - 0022-3263

VL - 82

SP - 1986

EP - 1995

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 4

ER -

Cooperative binding in a phosphine oxide-based halogen bonded dimer drives supramolecular oligomerization

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